CN102610810A - Lithium ion battery, anode sheet thereof, and anode material thereof - Google Patents
Lithium ion battery, anode sheet thereof, and anode material thereof Download PDFInfo
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- CN102610810A CN102610810A CN2012100440197A CN201210044019A CN102610810A CN 102610810 A CN102610810 A CN 102610810A CN 2012100440197 A CN2012100440197 A CN 2012100440197A CN 201210044019 A CN201210044019 A CN 201210044019A CN 102610810 A CN102610810 A CN 102610810A
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Abstract
The invention belongs to the technical field of lithium ion battery, and especially relates to an anode material. The anode material has two voltage platforms, wherein the voltage platforms are respectively in ranges of 3.0-3.9V, and 3.9-4.1V. In unit time, the voltage rising gradient of the 3.9-4.1V voltage platform section is smaller than that of the 3.0-3.9V voltage platform section. Compared to prior arts, with the anode material of different voltage platform section ranges, and with the correlation between the voltage and battery surface temperature increasing during a charging process, an anode material with which the voltage is slowly increased in a relatively high voltage platform range is selected, such that the battery surface temperature is slowly increased during a charging process, a phenomenon of excessive temperature caused by sharp temperature accumulation during a high-rate charging process is avoided, and battery surface temperature increasing can be effectively reduced. Also, the invention discloses an anode sheet comprising the anode material, and a lithium ion battery comprising the anode sheet.
Description
Technical field
The invention belongs to technical field of lithium ion, relate in particular to a kind of positive electrode that can improve lithium ion battery surface temperature rise in the big multiplying power quick charge process, and the anode pole piece and the lithium ion battery that comprises this anode pole piece that comprise this positive electrode.
Background technology
Along with the continuous development of modern electronic technology, lithium ion battery becomes the indispensable chemical power source of electronic product already with advantages such as its energy density are high, voltage platform is high, self-discharge rate is little and have extended cycle life.
Yet electronic product inevitably need use in specific hot environment sometimes, for example; The ambient temperature that global positioning system (GPS) is used even up to 100 ℃; And for example, in the notebook computer, lithium ion battery all adopts the battery pack that the many strings of battery are many and form at present; And in electric tool, the many strings of lithium ion battery are many and to form the application mode of battery pack more common.And this battery pack often all is sealed in the bad device of heat dispersion.This just causes battery pack in big multiplying power cyclic process, and battery surface temperature rise meeting becomes bigger, and the heat that battery surface produced can not in time leave, and finally causes the capacity attenuation also can be more and more faster.This is because under the hot conditions; The inside lithium ion cell side reaction increases; For example, positive electrode is to the oxidation of electrolyte, all can aggravate along with the rising of temperature near oxidation of the barrier film of positive electrode layer etc., and these side reactions all can cause the deterioration of cycle performance of battery.Even more serious is, battery also can flatulence be serious because of the long-term use in hot environment.
Some schemes have been proposed in the existing technology; To solve lithium ion battery too high problem of temperature rise in big multiplying power quick charge process; For example application number is that the Chinese patent of CN200910250941 adopts thicker collector (the for example aluminum foil current collector of the anodal 20～40um of employing) to reduce the battery surface temperature rise; Though this can improve the problem of temperature rise of lithium ion battery in big multiplying power quick charge process to a certain extent; But reduced the energy density of battery, therefore, limited its further use.
And application number is the Chinese patent of CN200910186470 a kind of three platform voltage positive electrodes have been proposed; Yet this positive electrode voltage platform scope is than higher; For reducing the control circuit that uses in the finished product battery; It is helpful to reduce the battery cost, but can not effectively improve the problem of temperature rise of the battery surface of battery in big multiplying power quick charge process.
In view of this, necessary a kind of positive electrode that can improve lithium ion battery surface temperature rise in the big multiplying power quick charge process is provided, and the anode pole piece and the lithium ion battery that comprises this anode pole piece that comprise this positive electrode.
Summary of the invention
One of the object of the invention is: to the deficiency of prior art, and a kind of positive electrode that can improve lithium ion battery surface temperature rise in the big multiplying power quick charge process is provided.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of anode material for lithium-ion batteries; Described positive electrode has two voltage platforms; Said voltage platform is respectively in 3.0-3.9V and 3.9-4.1V scope; And in the unit interval, the voltage rate of rise of 3.9-4.1V voltage platform section is less than the voltage rate of rise of 3.0-3.9V voltage platform.
A kind of improvement as anode material for lithium-ion batteries of the present invention; Described positive electrode has three voltage platforms; Said voltage platform is respectively in 3.0-3.75V, 3.75-3.9V and 3.9-4.1V scope; And in the unit interval, the voltage rate of rise of 3.9-4.1V voltage platform section is less than the voltage rate of rise of 3.75-3.9V voltage platform, and the voltage rate of rise of 3.75-3.9V voltage platform section is less than the voltage rate of rise of 3.0-3.75V voltage platform.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, said positive electrode is cobalt acid lithium (LiCoO
2), nickle cobalt lithium manganate (LiNi
xMn
yCo
1-(x+y)O
2), LiMn2O4 (LiMn
2-xM
xO
4), Li, Ni, Mn oxide (LiNi
xMn
1-xO
2) at least two kinds, wherein, x≤1, x+y≤1.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, said positive electrode is that the precursor of multiple compound carries out that high-temperature roasting is synthetic to be obtained.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, said positive electrode is that multiple compound obtains through physical method is evenly mixed.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, the surface of said positive electrode is coated with metal oxide.
As a kind of improvement of anode material for lithium-ion batteries of the present invention, said metal oxide is Al
2O
3, TiO
2At least a with among the MgO.
With respect to prior art, the present invention has following beneficial effect at least:
Battery is in big multiplying power quick charge process, and along with the carrying out in charging interval, battery surface temperature changing trend and voltage platform variation tendency exist mutual corresponding relationship.When voltage increases when very fast, the also corresponding increase of the temperature rise of battery surface is very fast; When the voltage increase was relatively slower, the temperature rise of corresponding battery surface also slowly increased.Adopt the positive electrode of the different electric pressing step segment limit among the present invention; Utilize the mutual corresponding relationship of battery surface temperature rise and voltage in the charging process; Select the interior voltage increase of high voltage flat roof area positive electrode slowly; Make that the battery surface temperature slowly increases in the charging process, avoid reducing the temperature rise of battery surface effectively because temperature is sharply piled up and the too high phenomenon of temperature that produces in the big multiplying power charging process.
Another object of the present invention is to provide a kind of anode slice of lithium ion battery; Comprise plus plate current-collecting body and be coated in the anodal diaphragm on the said plus plate current-collecting body; Said anodal diaphragm comprises positive active material, bonding agent and conductive agent, and said positive active material is the described anode material for lithium-ion batteries of above-mentioned paragraph.
With respect to prior art, anode slice of lithium ion battery of the present invention can improve the surface temperature rise of lithium ion battery in the big multiplying power quick charge process because its active material is the positive electrode with different voltage platforms.
Of the present invention also have a purpose to be to provide a kind of lithium ion battery; Comprise anode pole piece, cathode pole piece, be interval in the barrier film between said anode pole piece and the cathode pole piece; And electrolyte, said anode pole piece is the described anode slice of lithium ion battery of above-mentioned paragraph.
With respect to prior art, lithium ion battery of the present invention is owing to have the anode pole piece that can improve the surface temperature rise of lithium ion battery in the big multiplying power quick charge process, thereby can effectively suppress the oxidation reaction that takes place in the battery, improves the cycle life of battery.
Description of drawings
The curve that Fig. 1 at room temperature charges with the multiplying power of 0.5C for electric core in the embodiment of the invention 1;
The temperature rise comparison curves of electricity wicking surface when Fig. 2 charges with 1.8C under 45 ℃ for embodiment among the present invention 1 and Comparative Examples.
Embodiment
Below in conjunction with embodiment and Figure of description, the present invention is described in further detail, but execution mode of the present invention is not limited thereto.
Embodiment 1
The preparation of anode pole piece:
With positive active material cobalt acid lithium (LiCoO
2) and LiNi
0.5Mn
0.3Co
0.2O
2Mixture (mass ratio of the two is 1: 1), conductive agent conductive carbon (Super-P), bonding agent Kynoar (PVDF) and vanadium trioxide (V
2O
3) according to 70: 2: 3: 25 mass ratio is blended in the solvent N-methyl pyrrolidone (NMP), stirs, and obtains anode sizing agent.The anode sizing agent that obtains is coated on the aluminium foil that thickness is 9 μ m, and drying is colded pressing, and obtaining compacted density is 1.5g/cm
3Pole piece, pass through cut-parts, soldering polar ear again, obtain anode pole piece.
Wherein, cobalt acid lithium (LiCoO
2) the voltage platform scope be (3.60V～3.80V), LiNi
0.5Mn
0.3Co
0.2O
2The voltage platform scope be (3.80V～4.10V), during charging, cobalt acid lithium (LiCoO
2) the rate of rise of voltage platform section voltage in the unit interval be 0.58V/h, LiNi
0.5Mn
0.3Co
0.2O
2The voltage rate of rise of voltage platform section in the unit interval be 0.05V/h.
The preparation of cathode pole piece:
With negative electrode active material native graphite, conductive agent conductive carbon (Super-P), bonding agent butadiene-styrene rubber (SBR) and thickener sodium carboxymethylcellulose (CMC) according to 94: 2: 2: 2 mass ratio is blended in the aqueous solvent, stirs, and obtains cathode size.The gained cathode size is coated on the Copper Foil that thickness is 9 μ m, and drying is colded pressing, and obtaining compacted density is 1.7g/cm
3Pole piece, again through cut-parts, the welding negative lug, obtain cathode pole piece.
The preparation of electrolyte:
Methyl ethyl carbonate (EMC), diethyl carbonate (DEC), ethylene carbonate (EC), propene carbonate (PC) according to 1: 1: 0.5: 0.5 mixed is even, adds lithium hexafluoro phosphate (LiPF
6) as solute, make lithium hexafluoro phosphate (LiPF
6) concentration be 1M, process electrolyte.
Barrier film adopts polyethylene porous membrane, and the thickness of perforated membrane is 16 μ m.
The preparation of lithium ion battery:
The anode pole piece that obtains, cathode pole piece and barrier film are wound into battery in order, with battery closedtop and side seal, stay liquid injection port with aluminium plastic membrane.Then from liquid injection port perfusion electrolyte, again through changing into, operation such as capacity makes lithium ion battery.
Embodiment 2
Different with embodiment 1 is:
Positive active material is LiNi
0.5Mn
0.3Co
0.2O
2With LiCoO
2Mixture (mass ratio of the two is 1: 3), and LiNi
0.5Mn
0.3Co
0.2O
2With LiCoO
2The surface be coated with Al respectively
2O
3And TiO
2, the surface is coated with TiO
2LiCoO
2The voltage platform scope be that (3.60V～3.90V), during charging, its voltage rate of rise in the unit interval is 0.61V/h; The surface is coated with Al
2O
3LiNi
0.5Mn
0.3Co
0.2O
2The voltage platform scope be that (3.90V～4.00V), its voltage rate of rise in the unit interval is 0.22V/h.
All the other repeat no more with embodiment 1 here.
Embodiment 3
Different with embodiment 2 is:
During charging, cobalt acid lithium (LiCoO
2) the rate of rise of voltage platform section voltage in the unit interval be 0.63V/h, LiNi
0.5Mn
0.3Co
0.2O
2The voltage rate of rise of voltage platform section in the unit interval be 0.23V/h.
All the other repeat no more with embodiment 1 here.
Embodiment 4
Different with embodiment 1 is:
Positive active material is LiNi
0.6Mn
0.2Co
0.2O
2With LiMn
1.95Cr
0.05O
4Mixture (mass ratio of the two is 1: 5), LiMn
1.95Cr
0.05O
4The voltage platform scope be that (3.60V～3.90V), during charging, its voltage rate of rise in the unit interval is 0.61V/h; LiNi
0.6Mn
0.2Co
0.2O
2The voltage platform scope be 3.90V～4.00V, during charging, its voltage rate of rise in the unit interval is 0.08V/h.
All the other repeat no more with embodiment 1 here.
Embodiment 5
Different with embodiment 1 is:
Positive active material is LiNi
0.5Mn
0.5O
2With LiCoO
2Mixture (mass ratio of the two is 1: 5), LiCoO
2The voltage platform scope be that (3.70V～3.90V), during charging, its voltage rate of rise in the unit interval is 0.46V/h; LiNi
0.5Mn
0.5O
2The voltage platform scope be 3.90V～4.00V, during charging, its voltage rate of rise in the unit interval is 0.09V/h.
All the other repeat no more with embodiment 1 here.
Embodiment 6
Different with embodiment 1 is:
Positive active material is LiNi
0.5Mn
0.3Co
0.2O
2, LiMn
1.95Cr
0.05O
4With LiCoO
2Mixture (mass ratio of the two is 1: 2: 5), LiCoO
2The voltage platform scope be that (3.60V～3.75V), during charging, its voltage rate of rise in the unit interval is 0.60V/h; LiMn
1.95Cr
0.05O
4The voltage platform scope be 3.75V～3.90V, during charging, its voltage rate of rise in the unit interval is 0.16V/h, LiNi
0.5Mn
0.3Co
0.2O
2The voltage platform scope be 3.90V～4.10V, during charging, its voltage rate of rise in the unit interval is 0.08V/h.
Comparative Examples
Be with embodiment 1 difference:
Described positive electrode active materials has only 1 voltage platform scope: 3.60V～4.00V in charging process, wherein, this voltage section voltage rate of rise in the unit interval is 0.60V/h.
Other are identical with embodiment 1, repeat no more here.
The lithium ion battery of embodiment 1 is at room temperature carried out charging measurement with the rate of charge of 0.5C, and the gained test curve is shown in Fig. 1.
Can be known that by Fig. 1 in charging process, the lithium ion battery of embodiment 1 can be observed 2 apparent in view voltage platform scopes, wherein AB section voltage platform scope is 3.60～3.80V, and CD section voltage platform scope is 3.85～4.00V.Along with the carrying out of charging process, the voltage that the A point is ordered to B point voltage and C point to D is all rising, but that CD section voltage increases trend is slow than the AB section, and promptly the CD section platform voltage rate of rise is littler than the AB section platform voltage rate of rise.
The lithium ion battery of embodiment 1 and Comparative Examples is carried out charging measurement with 1.8C under 45 ℃, the temperature rise on test battery surface after charging is accomplished, and make comparison curves, as shown in Figure 2.
Can find that from Fig. 2 the temperature rise of embodiment 1 in charging process has significantly flex point, promptly this flex point is divided into 2 interval ranges with temperature; Simultaneously can also find that this temperature changing trend and voltage platform variation tendency have certain correlation, and have the characteristics of following aspect: in the charging process, steeper when voltage has just begun to rise, the battery surface temperature rise also correspondingly changes steeper; Voltage rises when slow, and the battery surface temperature rise is also corresponding to become slow.And have only a voltage platform scope in the Comparative Examples, the battery surface temperature rise can only be observed a temperature rise interval in the charging process.Embodiment 1 makes that owing to the slow variation of voltage in the CD section temperature rise variation of correspondence also becomes slowly in this scope among the present invention, has alleviated the too high phenomenon of temperature that battery produces owing to the rapid accumulation of temperature in big multiplying power charging process to a certain extent.
Lithium ion battery to embodiment 1 to 6 and Comparative Examples carries out big multiplying power quick charge test:
45 ℃ of multiplying power chargings of adopting 2C down, before the test, the test battery surface temperature is designated as T with lithium ion battery
1, after charging was accomplished, the surface temperature of test battery was designated as T immediately
2, and the temperature rise Δ T on counting cell surface, wherein, the Calculation of Temperature Rise formula is Δ T=T
2-T
1, the gained result is shown in table 1.
The temperature rise of the lithium ion battery of table 1: embodiment 1 to 6 and Comparative Examples
| Group | Temperature rise (℃) |
| Embodiment 1 | 9 |
| Embodiment 2 | 9 |
| Embodiment 3 | 14 |
| Embodiment 4 | 10 |
| Embodiment 5 | 11 |
| Embodiment 6 | 7 |
| Comparative Examples | 16 |
Can know by table 1; Adopt the positive electrode of multivoltage flat roof area; And this material is in the unit interval, and when the voltage rate of rise was less than the low voltage range section voltage rate of rise in the high voltage segment limit, the temperature rise of electric wicking surface was less than the temperature rise of having only a voltage platform scope.
This be because battery in big multiplying power quick charge process, along with the carrying out in charging interval, battery surface temperature changing trend and voltage platform variation tendency exist mutual corresponding relationship.When voltage increases when very fast, the also corresponding increase of the temperature rise of battery surface is very fast; When the voltage increase was relatively slower, the temperature rise of corresponding battery surface also slowly increased.
According to the announcement and the instruction of above-mentioned specification, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the specific embodiment that discloses and describe above the present invention is not limited to also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this specification, these terms are explanation for ease just, the present invention is not constituted any restriction.
Claims (9)
1. anode material for lithium-ion batteries; It is characterized in that: described positive electrode has two voltage platforms; Said voltage platform is respectively in 3.0-3.9V and 3.9-4.1V scope; And in the unit interval, the voltage rate of rise of 3.9-4.1V voltage platform section is less than the voltage rate of rise of 3.0-3.9V voltage platform.
2. anode material for lithium-ion batteries according to claim 1; It is characterized in that: described positive electrode has three voltage platforms; Said voltage platform is respectively in 3.0-3.75V, 3.75-3.9V and 3.9-4.1V scope; And in the unit interval, the voltage rate of rise of 3.9-4.1V voltage platform section is less than the voltage rate of rise of 3.75-3.9V voltage platform, and the voltage rate of rise of 3.75-3.9V voltage platform section is less than the voltage rate of rise of 3.0-3.75V voltage platform.
3. anode material for lithium-ion batteries according to claim 1 is characterized in that: said positive electrode is cobalt acid lithium (LiCoO
2), nickle cobalt lithium manganate (LiNi
xMn
yCo
1-(x+y)O
2), LiMn2O4 (LiMn
2-xM
xO
4), Li, Ni, Mn oxide (LiNi
xMn
1-xO
2) at least two kinds, wherein, x≤1, x+y≤1.
4. anode material for lithium-ion batteries according to claim 1 is characterized in that: said positive electrode is that the precursor of multiple compound carries out that high-temperature roasting is synthetic to be obtained.
5. anode material for lithium-ion batteries according to claim 1 is characterized in that: said positive electrode is that multiple compound obtains through physical method is evenly mixed.
6. anode material for lithium-ion batteries according to claim 3 is characterized in that: the surface of said positive electrode is coated with metal oxide.
7. anode material for lithium-ion batteries according to claim 6 is characterized in that: said metal oxide is Al
2O
3, TiO
2At least a with among the MgO.
8. anode slice of lithium ion battery; Comprise plus plate current-collecting body and be coated in the anodal diaphragm on the said plus plate current-collecting body; Said anodal diaphragm comprises positive active material, bonding agent and conductive agent, it is characterized in that: said positive active material is the described anode material for lithium-ion batteries of claim 1 to 7.
9. a lithium ion battery comprises anode pole piece, cathode pole piece, is interval in the barrier film between said anode pole piece and the cathode pole piece, and electrolyte, it is characterized in that: said anode pole piece is the described anode slice of lithium ion battery of claim 8.
Priority Applications (1)
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|---|---|---|---|
| CN2012100440197A CN102610810A (en) | 2012-02-27 | 2012-02-27 | Lithium ion battery, anode sheet thereof, and anode material thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100440197A CN102610810A (en) | 2012-02-27 | 2012-02-27 | Lithium ion battery, anode sheet thereof, and anode material thereof |
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| CN102610810A true CN102610810A (en) | 2012-07-25 |
Family
ID=46528051
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161756A (en) * | 2015-09-28 | 2015-12-16 | 广西师范大学 | Lithium iron phosphate lithium-ion battery with electricity exhaustion early-warning function |
| CN106558688A (en) * | 2016-11-18 | 2017-04-05 | 贵州振华新材料有限公司 | High-voltage lithium-battery cathode material, battery and preparation method and application |
| CN113488622A (en) * | 2021-06-30 | 2021-10-08 | 湖南立方新能源科技有限责任公司 | Positive active material, positive plate and preparation method and application thereof |
| CN113690479A (en) * | 2020-05-19 | 2021-11-23 | 北京小米移动软件有限公司 | Rechargeable battery and electronic device |
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| CN1595687A (en) * | 2003-09-08 | 2005-03-16 | 中国科学院物理研究所 | A positive electrode material for lithium secondary cell, and preparation and usage thereof |
| CN101409342A (en) * | 2008-10-31 | 2009-04-15 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing composite anode material |
| CN101740765A (en) * | 2008-11-17 | 2010-06-16 | 深圳市比克电池有限公司 | Lithium ion battery anode material and lithium ion battery prepared therefrom |
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| CN1595687A (en) * | 2003-09-08 | 2005-03-16 | 中国科学院物理研究所 | A positive electrode material for lithium secondary cell, and preparation and usage thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105161756A (en) * | 2015-09-28 | 2015-12-16 | 广西师范大学 | Lithium iron phosphate lithium-ion battery with electricity exhaustion early-warning function |
| CN106558688A (en) * | 2016-11-18 | 2017-04-05 | 贵州振华新材料有限公司 | High-voltage lithium-battery cathode material, battery and preparation method and application |
| CN113690479A (en) * | 2020-05-19 | 2021-11-23 | 北京小米移动软件有限公司 | Rechargeable battery and electronic device |
| CN113690479B (en) * | 2020-05-19 | 2024-01-30 | 北京小米移动软件有限公司 | Rechargeable battery and electronic device |
| CN113488622A (en) * | 2021-06-30 | 2021-10-08 | 湖南立方新能源科技有限责任公司 | Positive active material, positive plate and preparation method and application thereof |
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Application publication date: 20120725 |